Mixed polycarboxylic acid esters of alkylidene glycols and polymers thereof



Patented Sept. 30, 1952 TED. STATES? MIXED romesae'dxrue'gseintissues.be;j" 1

ALKYLIDENE, oLYooLs, i"j4N1i POLYMERS] L Theodore Evans, ak1and,-and-David EJAdelson, Berkeley, Calif., and Lynwood-N."Whitehill, .ChicagmgIlL, assignors to .Shelli Development Company, Emeryville, Calif, a corporationqofg Delaware g No Drawing. 'Application August 25,4951;

"Serial No. 243,764":-

. f1e "Claims (o1. aka- 1734;. 1,.

,The present invention relates. to a new class; of polymerizable unsaturated organic compounds; and to the polymers.thereof;, .More particularly,

the, invention relates ,toya novel group of polyvention further provides valuable Lpolymers ob-.

tainedLby polymerizing =thelaforedescribed mixed esters by themselves or in combination :withiother polymerizable ethylenically unsaturated organic compounds.

As a preferred embodiment, the inyention pro.- vides alpha-alkanoxy-ethyl esters i-of aliphatic.

' object to provide unsaturated esters thattare polycarboxylic acids, and preferably-alkanedioic and alkanedioic acids, and aryl ;polycarbo,xylic.= acids in whichone of the carboxyl-;.groups.is'esw terified by a betagammaeethylenically unsatu;

rated monohydric alcohol, e. g,,,'compounds.suohv as, ethylidene, acetate ,allyl..maleate,;.or alpha-i acetoxyethyl' allyl phthalata-and totheir homopolymersuand copolymers.

This application is a continuationrinepart of our, application Serial No.-' #738,496, filed. March 31, 1947, now abandoned. p 1 f 1 It is an object of the invention to provide a. new class of polymerizable unsaturated organic, compounds.- It; is-a further object. ;.to. provide novel unsaturated mixed esters of alkylidene. glycols and valuable polymers thereof. .It is a. -f urther object to provide'novel unsaturated mixed;v esters of alkylidene glycols. that possess many.- unique properties which ,make, them partied? larly useful and valuable in industry. --It is Ja further object to provide novel. mixed fllIlSfltur rated esters of ethylidene glycol that may be. polymerized; to produce polymers 'having many unusual and valuableproperties... Itisafurther particularly valuable 1 as plasticizers.-

Other: iobjects and advantages of *the iiinventioni will be. the..-following detailedzdescription" thereof.

apparent from It has -now been other objects .are accomplished. by thenovel,un-.:-

Saturated mixed-esters:-ofhtheinvention/comprise,- g 1 g esters ofant-alkylideneglycdlwwherein. oneiqfr' the hydroxyl groups-cor thepralkylidenea 'gg molecule. ha'sbeen iesterified with 'a monocar boxylici; acid 'andtthei dtherihydroxyl-zgroupeshasz been esterifiedcwith an acidester roffaipolycat-Q boxylicsacid'.and::'an= ethylenic'ally:unsaturated monohydric ialcohol sand polymers; thereofjobg, tainedby polymerizing stheL isaidtz esters b y them selves or-xwith. other polymerizableEunsatuiated compounds in avariety oft-proportions}.:rThe unique, structural: arrangement ofithese'ipa rfica-i; I ular.-; esters has been :found to endow the' said compounds with unexpected physical and ch'em'e ical properties which make -:them particularly 'onomeri'ct useful; and .valuable .bothi in: th'eiv p and polymeric form's: Certaim-ef .t eipolymers, 1' or example, exhibit propertieswhi-clrare inmany respeots'ftotally ,unlike..-the properties that could object to provide unsaturatedmixed esters .conm,

taining a plurality of unsaturated linkages that" may be polymerized to produce insoluble, infusi ble polymers having good, flexibility and are-v crack-free. It is a further objecttoprovide un=.-; saturated mixed esters o i: ethylidene glycol thatv may be polymerized to produce polymers having v improved stability to light andheat. Itis a-fur.-

ther object to'provide new-and -particularly use ful class. of polymeric material; It-is a; .fv .1rther of,- .i the properties; of- ;known compounds z having be; anticipated by: analogyfrom a1;considerations-.-

structural;similarities-. I 1

,The polymers prepared-from. the ."unsaturated mixed esters .of the' inventionswh-ich;possess 'a; I

plurality of polymerizable linkages a'have b'eenfound, for example,- to .have ltheaunexpectedcpropf erty of forminginsoluble. and infusiblelsolid poly-M s ,mers;which;are:not only. flexible and'entirely' crack.-f ree,3. but; vwhich exhibit marked; color .sta'

i iy aon' long exposure, to:dir'ectsunlight. Suchi polymers. are ideally suitedforuse-Lin preparing:

molded articles'i suchas; buttons; caps; igears,zetc: which mustbe strong-and be' jableut withstand-=1 s d r e 'Qfiside J pressure-2 .i-That polymers of these particular,::monomers.; possessed. such properties-was quite surprising;a.in-:.-view of-dthe -i. fact-;th,at-;,po1y1 ners preparedfrom other mono? ,mersy possessing .a plurality; "of non-conjugated polymerizable linkages, such as'diallyl phthalate;

as well as related ethylidene glycollmonome'r rr such as ethylidene.dimethacry1ate, are very b'rittlejand easily cracigedduei-rto the strainset uptwithin' the resinousimas'si during %the" curing proc ess. In addition',r;these=prion known polymers generally' possess poor -resistancef I to; heat and light and are: easily discolored whensexposedcforr.

extended. periods-of I time :.;t.'o? these-elements; .-The polymers prepared from itheaunsaturateda butyrate, and cellulose butyrate, and can be use to l fil'carbon atoms.v i Particularly preferred: monocarboxyl-i'c' .acids" are the. hydrocarbon monocarboxylic acids containing from 1 to 12carbon atoms,-andthe oxy; 55 'thio-, sulfinyl-.. and sulfonyle'substituted aliphatic hydrocar'bonj monocarboxylic, acids,- containing mixed esters of the invention which possess only a single 'polymerizable linkage have been found to possess an unexpectedly high degreeof com-.

patibility with common resinous materials, such as polyvinyl chloride, polyvinyl acetate, poly- 5 styrene, and the cellulose derivatives, such ass, nitrocellulose, cellulose acetate, cellulose acetate in combination therewith as plasticizers or resin additives.

' The unsaturated mixed esters of, the invention;

haveboiling points which, are in ge'neral well above 100 C. at pressures ofl mm; orless'and exhibit wide ranges of miscibility "andcompatibility with coating solvents, lubricating stocks, resins, etc. and are suited for use as plasticizers,

,lubricating oil additives, asphalt adhesive agents, -water-proofing agents for silica-gel greases Pour 7 point depressants, viscosity index improvers", textile lubricants, and resin lubricants or plasti: vcizersr: a L r The unsaturated miXed esters'of therpresent. {invention may-be describedasesters of an alkyl ;i'dei 1e zglycol,' such-as1 ethylidene glycol, wherein ,l "one of the hydroxyl groups has been esterified with amonocarboxylicnacid and the other hydroxylzwgroup. has be'en esterified-with' .an acid ester of -a :polycarboxylicf acid and an ethylenicall-y unsaturated monohydricalcohol.

' The monocarboxylic acids used to esterify one .-of,the -hydroxyl groupspofxthe 'alkli'dene .gly'c'olmolecule may be. saturated, unsaturated, 'aliphat 10,,:alicyclic,ll-heterocyclic .or aromatic and may be fsubstitutedjif'fdesired with-non-interfering' fsubstituents, suchas' halogen atoms,"alkoxy"radilcals', and the like; ,The acids may also contain oxy, thio. sulfinyleorsulfonyl link'ageswithin their :molecule. Illustrative examples of the1mono- 1 carboxylicwacids are .zacetic, propionic, caproic, butyric, 'valeric, enanthicgacrylic, caprylic, :meth- 4'0 acrylic, pelargomc;-:.capric, ,lauric, myristic, pal-- ,initicf, stearic, ,arachidic, :an'gelic, sorbic; hydrosorbicarz-octenoic, 2;8.-decadieno'ic, cyclohexanoic,

- cyclopentenoic, '1 picolinic, nicotinic," beta-ketobutyric', 2-'nitropentanoic, .3-hyd-roxypentanoic, '-45 -cyclohexaneacetic,l. cyclohexanoic, methy'lthiopropioni'c butylsulionylpropionic," benzyloxyace tic, ethylhexyloxyacetic, ..cyclohexyl-thiopropionic,

phenylthioacetic, and chlorophenylthiopropionicacid. :Preferred 'monocarboxylic 'acids'are the aliphaticmonoc'arboxylic acids containing from fronr-l; to 14 carbon) atoms such as acids'of thecformulaRCOOI-I; RORCOOH, RSRCOOHJ hydrocarbon radical. -Especiallypreferred-monocarboxylic acids are 'the 'alkano'ic acids and alv .kenoio'acids containing from 1'to.6 carbon atoms, the valkyloxyalkanoic acids, alkylthioalkanoic' acids, alkylsulfinylalkan'oic acids, andthe'alkylsulfonylalkanoic acids containing from 1- -to.'8'v i carbon,atoms'.==

-Of special; interest,'iparticularly because of the, fine quality of the polymerstprepare'd from the resulting esters, arethe al-kenoic acids, preferably m containing fromel toz6carbon atoms.

The other hydroxyl' group "on the 'alkyliden lycol moleculesis esterified with 'anacid ester "-of apolycarboxylict,acids'and an ethylenically un- -i V saturated monohydric alcohol. The "polycarboxylic acids used in producing these acid esters may contain two, three, four or more carboxyl groups and may be saturated, unsaturated, aliphatic, alicyclic, heterocyclicj or aromatic. They may also be substituted if desired with non- ,interfering substituents, such as halogen atoms, 7 alkoxyradicals, and the like. The polycarboxylic acidsinay. nd in some cases preferably do, contain oxy, thio, sulfinyl or sulfonyl linkages within their molecule. Illustrative examples of the vlpolycarbo xylic acidsare malonic, succinic, adipic,

pimelic, ketopimelic, suberic, azelaic, brassylic,

sebacic, dibromosucoinic, chloroadipic, maleic, I fumaric, glutaconic, alpha-hydromuconic, glutaric, alpha,beta'- diethylsuccinic, 2,5 heptadi enedioic, 3,-hexyne'dioic, 1,1,5-pentanetricarboxylic, ,-'5-octene-3,3,6-trioarboxylic, tricarballylic,

wherein R is a hydrocarbon radical. Especially' preferred polycarboxylic acidsare the aryl dicarboxylica'cids containing from 8 to 14 carbon atoms'wherein'the carboxyl groups are attached directly "to the aromatic ring, the alkanedioic M acids containing from 2.=to 10 carbon atoms, the

alkenedioic acids containing from 2 to 10 carbon atoms, the oxydialkanoi'c' acids, the thio'dialkanoid-aci'ds, :thesulfinyldialkanoic acids,and the I sulfonyldialkanoi'c acids containing from 217010- carbon atoms.

Of special interest,'particularlybecause ofthe fine q'uality'of'the polymers prepared from-the. resulting esters, are the unsaturated dicarboxylicacids, such as maleicacid, 'fumaric acid, and the like, and more particularly the alkenedioic acids containing "from 2 to'10 carbon atoms.

i The'un'sa'turated alcohols used in producing-the acid esters of the above-described polycarboxylic acids are. those monohydric" alcohols containingat least one polymerizable ethylenic linkage, pref: erably not more than four carbon atoms removed from the terminal'hydroxyl group. Particularly preferred al'co'holsto be used for this purpose are the allyl-type alcohols, i. e., the beta,gamma-- ethylenically unsaturated monohydric alcohols.

These alcohols may be exemplified by allyl al- .cohol, crotyl 1 alcohol, tiglyl alcohol, 3-chloro-2' buten-l-Iol, cinnamyl alcohol, 2,4-hexadienl -ol, 2-methyl-2-hexen-l1-ol', '5-'chloro-2 octen-1--ol, L3

cyclohexyl-2-octen-1-01, eephenyl-z-hepten l-ol, .2,4=dichloro-2-hexen=l ol; "and 3-ethyl'-2-octen- 1 01; Particularly preferredalcoholsto be used are the beta,gamma-'ethylenically' unsaturated aliphatic monohydric alcohols containing from *3 .to l 5 carbonf'atoms'] "Of special interest'are the aiken 2ols containing from 3' to 8 carbon atoms. 1

V la he QIX a Y Q ha r than we carboxyl groups, the carboxyl groups other than thefi ee carboxyl group, and the, one est'er'ifid} with the above-described unsaturated "alcohol maybe esterifled with thesaine ordiffe'rent' unsaturated alcohol or a; saturated monohydric a1- cohol, such as methanol, ethanol, butanol, amyl alcohol, octyl alcohol, decyl alcohol, ahdthe like.

Preferred saturated alcohols to be used forfthis purpose; are the alkanols containing from 1 to 8 carbon atoms.

The acid esters used producinglthe noyel' the unsaturated alcohols or one or more-of the unsaturated alcohols and the above described saturated alcohols, Examples 01 such acid esters include allyl hydrogen v maleate allyl hydrogen succlnate, allyl hydrogen adipate, allyl' hydrogen phthalate, methallyl hydrogen glyc ol ate, chloroallyl'hydrogen thiodipropionate, Z-hexenyl hydrogen oxydipropionate, 2-butenyl hydrogensulfonyl-dibutyrate, methallyl. hydrogen suliinyle dihexenoate, allyl butyl hydrogen 1,3,5-pentane: tricarboxylate, and the like.

. The novel unsaturated mixed esters of thefi ng vention are the esters of an alkylidene; glycol wherein one of the hydroxyl groupshas been es:- terified with any one of the above-described monocarboxylic acids and the other hydroxyl group has,

been esterified with any one of the above-- described, acid esters of the polycarboxylic acids and the unsaturated alcohols. Examplesof the v novel mixed esters include Ethylidene propionate allyl oxalate] Ethylidene propionate ethallyl methylsuccinat'e" Ethylidene butylate allyl adipate Ethylidene formate allyl sebaciate I Ethylidene' acetate methallyl naphthalenedicarboxylate r Ethylidene iormate methallyl succinate Ethylidene butyrate methallyl adipate v f Ethylidene butyrate allyl azeliate Ethylidene butyrate ethallyl methyl phthalate Ethylidene acetate allyl oxalate Ethylidene acetate allyl succinate J Ethylidene propionate methallyl glu'tarate- Ethylidene butyrate ethallyl pimelate v Ethylidene formate meth'allyl 'azeliatej Ethylidene propionate methallyl hydrophthalate Eth'yliden'e butyrate methallyl methylmaleate Ethylidene acetate allyl glutaconate Ethylidene formate allyl glutaconate Ethylidene propionate p'enten-l-ol-3 glutaconate I Ethylidene propionate 3 methyl penten-1-ol-3- glutaconate Ethylidene acetate diallyl "boxylate, I

Ethylidene acetate allyl butyl l,3,5-'-penta'ne-trifcarboxylate r H Particularly preferred unsaturatedesters of'the present invention are those containing at leastsaturated monohydric alcohols. Another group of such compounds comprises the alkylidene glycol mixed esters of saturated monocarboxylic acids and the acid esters of polycarboxyl'ic acids 1,3,5 pentane- ,tricar- Ethylidene' acetate diallyl 1,3,5 pentane' 'tric'a r-' boxylate Ethylidene'propionate dimethallyl 1,2,4 hexa'netricarboxylate 1 a i Ethylidene acetateallyl'maleate Ethylidene propionate'allyl maleate I Ethylide'ne acetateallyl dimethylrnaleate it Ethylidene butyrate allyl dimethylmaleate Ethylidene acetate di'm'e'thall-yl dimethacrylate Ethylidene'butyrate-allyl-citraconate w Ethylidene'acetate ethallyl citraconate Ethyl-ide'ne dimethylacetate methallylitaconate Ethylidene acetate buteh-l-ol-B ita'conate" Ethylidene acetate 3 -methyl pe'nten-l-ol-S ita "conate" Y I Ethylidene propionate allyl dimethacrylate Ethylidene formate methallyl'dimethylacrylate Ethylidei e 'acetatehepten 1 ol-3dimethylac'rylate-*"m Ethylidenepropionate methallyl ethylmaleate Ethylidene acetate allyl ethylmaleate Ethylidene butyrate 'tiglyl ethylr'naleate Ethylidenebutyrate ethallylmethylnraleate ogttti'nifizha are the unsaturated mixed esters of the general formula oooRoooI u:

cmo

o'oom wherein Riis abivalent'aliphatic or aromatic li y drocarbon radica'hsuch'fas a bivalent alkyl, alkenyl or aryl radical,,R1 is an alkenyl radical, pref-- erablynot-more than six carbon atoms, and R2 is a hydrocarbon radical, and preferably an alkyl, alkenyl or aryl radical;

The unsaturated mixed esters of the may. be preparedv by a variety of n' iethocls;v A

method that" has been found particularly suitable for use in preparing the novel mixed esters cornprises reacting (1) an acid ester of a polycarboxylic acid. with (2) an ester of an ethylenically unsaturated monohydric alcohol and a'monocarboxylio acid in the presenceof an acid ca talystand preferably in the presence of a polymerization inhibitor. .This method of preparation may be illustrated by the following reaction showing the [preparation of eth ylidene acetate allyl sue-- hydrogen succinate with.

bility that the formed unsaturatedmixedesters mayundergo-decomposition by splittingout amolecule of the monocarboxylic acid to form a poly unsaturated ester. Thus, ethylidene acetate allyl succinate may undergo decomposition to form acetic acid and vinyl allyl succinate. Care should therefore be taken during the reaction; to, prevent or minimize this type of decomposition.

The decomposltionmaybe prevented or greatly unsaturated monohydric a lcohols, I

7* reduced bycontrolling t""e"r'eaction period: and the reactiontemperature' and/or by avoiding any removal of "the-decomposition products as 'indi-- cated in detail below.

Theacid esters of the polycarboXyli'c acids" used in this reaction may be any of those; described hereinabove' in the section dealing with thef'description of the novel esters of the invention. The esters of the monqcarboxylic acids ,to be employed maybe any. of those'obtained byesteri fying any of the above-=described monooarboxylic acids and any of the above-described unsaturated monohydric alcohols, and Preferably ,the il-al-' kenols, such as vinyl alcohol and the-like;

A wide variety of catalysts maybe ised in the process. In general, the most desirable catalyst are those that have been used in the iormation of vinyl esters from acetylene. Particularly suitable catalysts are the acids, such as sulf-uric acid, phosphoric acid and silicotungstic-acid, and these acids used in conjunction with metal-compounds, such as mercuric salts, copper acetate, vanadium pentoxide, ferric dichromate ierric; oxide, ceric acid sulfate, and'the like. Es'pecially preferred catalysts are the mercury;,-salts of the strong acids. For thebest resultsathese catalysts are prepared directly in the reaction solution by initially introducing the mercuric salts, such as mercuric acetate, and then add- 1 ing the strong acid to convert thesalt, into the desired salt .of the strong. acid. ep n ng. part on the particularicatalyst forming acid-used, it may be of'ladvantage to addless of the acid than is required to form the normal mercury salt,

, and as little as ha'lf'of this quantit'y has" been used successfully. At the same time an excess of the acid may in some instances be desirable. Other acids that may be used in preparing these mercury salts include phosphoric acid, silicotungstic acid boron trifluoride-carboxylic acid, and other heteropoly acids; Hydrochloric acid may be used m mne reactions. I

Suflicient catalyst should be'u'sed to insure that l the reaction will be accomplished in thedesired' themonoc'arbox'ylic acid over the'acid ester.

Preferably the unsaturated ester of uiempfioca'r: boxylic 'acidand the acid ester are combined in a mole ratio of 8:1 to 4: 1, and morei'prefer-ably' in a ratio of 7:1 to :1.

It is desirable in most cases to accomplish the 'esterification in the presence of a polymerization inhibitor, such as coppe'rbronzepowdensub fur, p-phenylenediamine, hydroquinone', tannic' acid and 'variousamino and sulfur compounds. These; inhibitors may be subsequently removed by washing, distillation, extractionandthe'like'.

The temperatures employed" in' there'actioh should not be excessive as high tmpefatu favorthe decomposition ofthedesired'mixedu saturated esters as indicatedabovef The rea tion can" generally be conducted at the" reflux esters of saturated alcohols, etc., andfioth causineiicessive decomposition but; teni a Preferred tem era ures muse from roonr t pe'rat'ure tofQO" G1; andfrhore' 'pi'eferalol' so cpt' vo fci "At OSpl' rifsuperat or subatmosp ene pressure may be used-as The'reaction should" sobe relatively shpr as to avoidiaeessive decomposing git-tn xiiisaturated mixed esters. In most instancsf the reaction period-should o be e cesses 3.5 hours.- Preferred reactionperiods rang'e mm: .5 to 2;.-s*hours; V I

' care should alsd-Joetoavoid any remo'val t produots,;'*such as-tnemoimcarbo'xyue acid-which would "tend to drive the" decbli'i'posi tion" reaction w 'h r ij y At'the'iend of the react-ion period," the activity of theeataiyst may be 'reduced or dstrcyd'bifi the'additidn or suitable additive's -such as sodi um acetateyand uiereaeuo mixture may their be subjected to aseparation process to recover the desiredmixed unsaturated' esters. If the separationis accomplished by distillation; the novel unsaturated mixed" esters of the hive" tion will probably be recovered as' thehig boiling residues, while; the decomposition products andunreacted components will generally berecovered-atthelower'temperatures;

"Thenovel unsaturated mixed di'e'sters' of the invention are relatively colorless m'obil was: cous' liquids or semi-solids. The'es'tersha'v'e boil ing points which are in general above --C.- at pressure =of 1' mm; or less' and they exhibit- Wide ranges of miscibility and-compatibility with various oils, resins and the like. They have e gcellent compatibilitywith polymers such as poly 1' vinyl chloride; polyvinyl esters, suchas'polf nyl acetate, cellulose esters, such as'cellulos'e'ao' cellulose ethers, such as ethyl cellulose, and, v methyl methacrylate, polystyrene and mare 'e iicellent plasticizers for these materials; Ast indicated above, they, are also of value'a's lubri eating oil additives; asphalt adhesivea'gehtsi pour" point depressants, etc. The novel unsaturated mixed esters of t vention are particularly valuable in' the preparation of polymeric 'mater'ials asi they ca ne pow: merized' alone or copo'ly'merized Withoth pea merizable organic compounds to produce val i' f able polymeric material. Monomers'to Becopo merized withthee'sters include the vinyl'n iono mers' containing a polyinerizable ethyle nic link;

age, such as styrene, vinyl ha'lides, 'vinylide ef" halides, vinyl esters of-prganic, acids, meth y l' methacjrylate, methyl acrylate', allylihalide'si '81 lyl esters of organicacids; olefinic 'organicacid f q 'i rnerizable compounds containing inthe one or more polymerizable organic rad'i one-or a plurality of' inorganic radicals" orfe l ments such as vinyl, allyl, metallyletcgesters of; phosphoric; acid, ortho acids of silicon, boron,

etc;,, asf well as compounds containing a plurality' of conjugated polymerizable' carbon to cai'bon '9 groups the compounds of thepr'esent invention are miscibleover" a wideran e. of proportions andv therefore undergo interpolymerizationfwith the majority of polymerizable compounds, thus forming polymers containing a residue of each of the monomers. However, in certain casesflnovel and valuable effects are obtained by exceeding the miscibility range of the monomers, thereby forming copolymerization products in which in-, terpolymerization occurs to a more or less limited extent. The compounds of the invention may also be separately partially polymerized ormixed with partially polymerized monomers of another material followed by the completion of'the copolymerization, or copolymerized by any of the various other techniques commonly-practiced I in the art."

The oxygen-containing polymerization cata lysts' are effective in accelerating'the polymerization of the compounds of the invention." Illustrative examples of such catalysts are benzoyl peroxide, acetyl peroxide, acetyl benzoyl peroxide, lauryl peroxide, dibutyl peroxide, 'succinyl peroxide, sodium peroxide, barium peroxide, tertiary alkyl hydroperoxides such as tertiary butyl hydroperoxide, peracetic acid, perphthalic acid, perborates, ozone and oxygen. Another class of polymerization catalysts which are effective is the di(tertiary alkyDperoxides'such as di(tertiary) butyl peroxide. be accomplished in the presence of mixtures of polymerization catalysts as; benzoyl peroxide and hydrogen peroxide, for example, or itmay be accomplished in the presence of both a catalyst and a polymerization inhibitor.

The polymerization maybe readily accom-- plished at moderately elevated temperatures, the

The polymerization may tion of the fusible polymer from the unreacted monomer by selective solvation. The fusible polymer may also be separated by distillation at reduced pressures, preferably in thepresence of a polymerization inhibitor, and may be stored in the'p'resence of the inhibitor for long periods of time.

The separated fusible polymer may be transferred to amold, applied as a surface coating, or given any-desired shape employing the methods common to the art such as dissolving or dispersing the polymer in a solvent or swelling agent. The second step or completion of the polymerization reaction may then be accomplished by the application of heat, light, pressure, in general, by the reapplication of the conditions, or *usually slightly more severe conditions than were applied to accomplish the partial polymerization. Inmost"cases sufilcient polymerization catalyst will remain'occluded in the fusible polymerto i accomplish the infusibilization polymeriz'ation, but wherever it is i practical or desirable,

' additional amounts of the; same or a different catalyst may be-emplo'yed. In certain cases} such as extrusion, injection or transfer molding, or the like, the steps of shaping and infusibilization of the fusible polymer will occur concurrently and the unsaturated esters of the invention are therefore particularly'adapted to molding methods of this general type.

Illustrative examples of the preparation and polymerization of certain of the compounds of the invention are given below; it is to be underrange of temperatures between about 60 C.=,and

150 C. bein particularly effective. In certain cases polymerization may be energized by light. The monomers may be polymerized while dispersed in a solvent, which is preferably immiscible with the catalyst, or may be polymerized in solution, in mass, or, in certain cases, in the vapor state. The process may be conducted continuously or intermittently and at normal, re'-" duced or superatmospheric pressuresunder the normal atmosphere of the room or under a blanket of an inert gas. The polymerization may be interrupted before completion, thus resulting in the formation of partialpolymers which are usually viscous somewhat fluid masses suitable for transferring to molds, or for impregnating porous materials and the like prior to completing the polymerization to solid plastic materials. a

The novel esters of the invention which contain two or more polymerizable olefinic linkages may be first polymerized into a polymer OfSllb'. stantially a linear structure and the polymerization interrupted at this point. While the polymerization normally continues to form insoluble infusible solid polymers by the formation of in-;

terlinkages between the chain, it is often advantageous to interrupt thereaction at the first step and form the soluble and fusible linear polymer into the desired shapes before completing the polymerization. The interruption of the polymerization reaction may be accomplished by any suitable method, such as a sudden cooling of the polymerizing mass by introducing a cold solvent into the reaction mixture. When the polymerization is arrested by the addition of diluent, it is advantageous to select a solvent for the monomer in which the fusible polymer is insoluble, thereby readily accomplishing the separastood, however, that the examples are given for the purposes of illustration only and the invention is not to be considered as limited to the particular details recited in the examples.

Example I 'tivity of the catalyst reduced byshaking the mixture with21 parts of sodium acetate, and .then filtering. Vinyl acetate was then removed at the end of process by distillation'under re duced pressure and the residue dissolved in carbon tetrachloride. The carbon tetrachloride solution was washed with sodium carbonate, dried over sodium sulfate and distilled under reduced pressure in the presence of 2.parts of tannic chloride. The first fraction recovered at 46 C.

(0.25 mm.) was identified as allylvinyl maleate.

Percent carbon:

. 54.6(9) Found "r 54.6(1) Calculated 54.6 Iodine number (Wij Found l. 14-115 Calculated 105.

- eese; I

f action containing .thefdesired mixed ester was 3? i- ,7 1 view? 4. 9 1 1w" a stein-i. bin e Found L illation a clear white liquid was recovered'at f eehov -des ribe Presses w ie e sd 5 .95 smas m oil /sh ne'a die'r eqi enem= 19 pe'rature 69 or "I'hejforma'tion r the aecoim 95 .n n b ilet iii were w e f lc m1... reduced under such conditions EsteFr tangm equivalents per 100 grams ofisample' 1" "m. I. 1 u l V M A Calculated i Refractive index, 12 1,5040 E a le .11 v e M Acidity in equivalents per grains of sarnplefiu 0.042 and dogs e ab e o e s was epeated s ns a eec -A sheetof ethylidene acetate allyl maleate was time of only about 1 hours and a reaction teni; cast t 65 -n o 1.44 hours n hepresence 91- P 3 3 26. of a outfifi C The o mati o th percent by weight of ,henzoyl peroxide.v The re; alkyl vinyl phthalate s greatly reduced under ultant-pol m r' as f u dto have aee ime fi u h on Y only 5.7 hours and formed a transparent infusible The, process was-repeated with the use of. the and insoluble coating wl ich was entirely free of following catalysts. The amount of the ethyl{ ksl d Xh b Qd arema kah e 9 Stab y idfinfi acetate allyl phthalate recovered in each under. the influence of direct sun ight. The. physcase isshown in the last column. a v

- "at It 1 I 11 ene I I v No. Catalyst Hrs. R, ei lux lacetate aliyl ice -prq srties f he res tant sti ne are; l sted.

d ew qmpr s i nstr n ths. Percent deformed at ultimate'po Yield point on-compression Percent deforrped at yield p I Example. I V

The ethylidene acetate allyl phthalate pro; duced inl'the above'examnle. is rnixed with 2j% ben'z'oyl'fperokide'ancl'h ed at 65 C. forfover.

Flexuralstrength 8,300 i v l]\)lodulutsinflexure s LXIO M I 144 hou The resulting. polymer:- was. a viscous.

st sl e mpact w s a. J Rockwell hardness; M scale 103 w hwdsz m a bl n l I Bercenttransmis on at 42 m, 7. r Y ride) and nitrocellulose. I e' entt en m 2. HIM-M 67 .F. .QQX,e?SP-QUI todirectsunlight Percent transmission at 425m, 1 fi8after 35fdaysexposure Example. V D I 1 f e xeq sueli ht ensity,204 Refractive index, am; 1.49 57- v I a 41 8???9 Pe i 9 9 qii w 1. 1mi? n r at v dispersion noxlg- 17s n ph te, 0 oles of vinyl formate, 3 parts hb gh ansm ssious e measp'i dr iefia gfifi ii gs of talnnieacid. 19 pa ts of mercuric acetateand eateri s;is-assess;assis ants; at: 5 a e. Q: 9%. we e as was arias, a th'ese c'gnditions. about 2 hours at ormal atmospheric pressure. E gm p q Theactivi tyfof" the catalyst 'w saestm'yejatv A nizgture contai in 1Q nolesoiallylhydro; treating Withsodiuin'actate and the mixture genfphthalatafioinoles;of vinyl acetate, Ziparts was allowed to stand Mermght -ahe m'iiiture of, 's'tannic chloride; 19.2 par ts of ne'reuricjacewas distilled to remove the vinyl format and fate and i l. 'parts ot 90 s'j1lf uric e l d 'v'gasjr'ethe: resdlie then dissolved in isopropyl et I and: fiuxed for 2 hours atnormal atmosp i c pres Washed free of-acidwith potassium carbon 'e f'sosure. The mixture was then cooled and allowed lut'ion. The ether soltuion was' 'then dried over to stand overnight. The resulting product was calcium chloride anddistilledf The first reaction then mixed with 21 parts of sodiumacetate to de- 5 removed comprised allyl vinylphthalate and the stroy the activity of the catalyst and the mixture desired ethylidene" formatehl-l yl phthalalte' was was filtered. Vinyl acetate was then removed by rei'IiOiied t n'Xli ac n is a high Boiling distillation under reduced pressure and the resisubstantially colorle'ssl-iquid." due was dissolved in isopropyl ether and washed m filmed l Obtained by replacing, fre'eof a eid with potassium carbonate solution. the l y y rog Dhthalate in the abet eerie The ether solution was then snea er/er sneium s ribeq pr c sswithequivalent amountsofash chloride and distilled. The vinyl'acetate was ret f l n acidi s tannin iydi-ejfif moved by flash distillation at 90"' ""Thefriekt adipat elchloroallyl hydrogen "manages-he fraction boiled at 104 to 106 C. at and enyl 'l ydrogen ghxtgraltefaihd 2 was identified as allyl vinyl phthalateT The last gen chloro'succina't.

Example VI dried and distilled. The first product removed comprised allyl vinyl phthalate and then the desired ethylidene propionate allyl phthalate was removed in the next fraction as a high boiling substantially colorless liquid.

Example VII A mixture containing 9 moles of allyl hydrogen thiodipropionate, 50 moles of vinyl acetate, 3 parts of tannic acid, 19 parts of mercuric acetate and 5 parts of 90% sulfuric acid is refluxed for 2 hours at normal atmospheric pressure. The catalyst is destroyed as in the previous example and. the mixture distilled to remove the vinyl acetate. On further distillation, allyl viny1 thiodipropionatcv is recovered, and then ethylidene acetate allyl thiodipropionate is recovered in the final fraction.

The ethylidene acetate allyl thiodipropionate produced above is mixed with 2% benzoyl peroxide and the mixture heated at 65 C. The resulting polymer is a viscous liquid that is soluble in a variety of solvents and is compatible with poly(vinyl chloride).

Unsaturated esters having similar properties are obtained by replacing allyl hydrogen thiodipropionate in the above process with equivalent amounts of each of the following acid esters: allyl hydrogen sulfonyldipropionate, .ally1 hydrogen sulfonyl dibutyrate, 2-hexenyl hydrogen thiodioctanoate, and 2-octenyl hydrogen thiodibu-- tenoate.

Example VII Ethylidene propionate allyl diglycolate was produced by heating a mixture containing 9 moles 3. A mixed esterwhich may be represented as a diester of anethylidene glycol wherein one of the hydroxyl groups of the ethylidene glycol molecule has been esterified with a saturated monocarboxylic acid containing from 1 to 15 carbon atoms and the other hydroxy group has been esterified with an acid ester of an ethylenically unsaturated dicarboxylic acid containing 2 to 18 carbon atoms and an ethylenically unsaturated monohydric alcohol containing from 3 to 15 carbon atoms.

4. A polymer of the mixed ester defined in claim 3. g

5. A mixed ester which may be represented as a diester of an ethylidene glycol wherein one of the hydroxyl groups of the ethylidene glycol molecule has been esterified with an alkanoic acid containing from 1 to 4 carbon atoms and the other hydroxyl group has been esterified with an acid ester of (1) a dicarboxylic acid containing no more than 15 carbon atoms and being selected from the gro'ilp consisting of acids of the formulae HOOCRCOOH, HOOCRORCOOH,

HOOCRSRCOOH, HOOCRSORCOOH.

6. A polymer of the mixed ester defined in claim 5.

7. A mixed ester which may be represented as a diester of an ethylidene glycol wherein one of the of allyl hydrogen diglycolate, moles of vinyl -pr0pi0nate, 3 parts of tannic acid, 19 parts of mercuric acetate and 5 parts of 90% sulfuric acid at 90 C. for 2 hours, and then removing the products as shown in the preceding example.

Similar esters are obtained by replacing the allyl hydrogen diglycolate in the above processclaim 1.

catalyst, vinyl propionate and decomposition hydroxyl groups of the ethylidene glycol molecule has been esterified with an alkenoic acid containing from 1 to 8 carbon atoms and the other hydroxyl group has been esterified with an ester of (1) a dicarboxylic acid of the formula HOOCRCOOH wherein R is a hydrocarbon radical, and (2) an alkenol containing notmore than 6 carbon atoms.

8. A mixed ester which may be represented as a diester of an ethylidene glycol wherein one of the hydroxyl groups of the ethylidene glycol molecule has been esterified with an alkanoi'c acid containing from 1 to 8 carbon atoms and the other hydroxyl group has been esterified with an acid ester of an alkenedioic acid and an alkenol containing not more than 6 carbon atoms.

9. A polymer of the mixed ester defined in claim 8. 3 10. Ethylidene acetate allyl maleate.

11. Alpha-acetoxyethyl allyl phthalate.

12. Ethylidene propionate allyl phthalate.

13. A polymer of alpha-acetoxyethyl' allyl phthalate.

14. A polymer of ethylidene acetate allyl maleate.

15. A polymer of ethylidene propionate allyl phthalate.

2. A polymer of the mixed ester defined in 16. An infusible insoluble polymer of ethylidene acetate allyl maleate.

' THEODORE W. EVANS.

DAVID E. ADELSON. LYNWOOD N. WHITEHILL.

REFERENCES CITED The following references are of record in the file of this patent:

Organic Chemistry. Fieser and Fieser. 2nd ed., Heath 8: 00.. Boston (1950), page 32. 

14. A POLYMER OF ETHYLIDENE ACETATE ALLYL MELEATE. 